Azo dyes whose diazo and coupling components stem from the thiazole series

ABSTRACT

Thiazole-azo dyes of the formula ##STR1## where R 1  is C 1  -C 12  -alkyl, which may be interrupted by oxygen atoms, phenyl, halogen, cyano or C 1  -C 4  -alkoxycarbonyl, 
     R 2  is formyl, cyano, C 1  -C 4  -alkoxycarbonyl or a radical of the formula --CH═CX 1  X 2 , where X 1  and X 2  independently of each other are cyano or C 1  -C 4  -alkoxycarbonyl, 
     R 3  is C 1  -C 12  -alkyl, which may be interrupted by oxygen atoms or substituted by phenyl or phenoxy, C 5  -C 7  -cycloalkyl, substituted or unsubstituted phenyl, furyl, thienyl, C 1  -C 4  -alkylthienyl or pyridyl, and 
     R 4  and R 5  independently of each other are C 1  -C 12  -alkyl, which may be interrupted by oxygen atoms and/or substituted, 
     with the proviso that in at least one of R 1 , R 4  and R 5  the alkyl chain is interrupted by oxygen atoms, are useful for dyeing textile fibers.

The present invention relates to novel thiazole-azo dyes of the formula I ##STR2## where R¹ is C₁ -C₁₂ -alkyl, which may be interrupted by from 1 to 3 oxygen atoms, phenyl, halogen, cyano or C₁ -C₄ -alkoxycarbonyl,

R² is formyl, cyano, C₁ -C₄ -alkoxycarbonyl or a radical of the formula --CH═CX¹ X², where X¹ and X² are identical or different and each is independently of the other cyano or C₁ -C₄ -alkoxycarbonyl,

R³ is C₁ -C₁₂ -alkyl, which may be interrupted by from 1 to 4 oxygen atoms or substituted by phenyl or phenoxy, C₅ -C₇ -cycloalkyl, substituted or unsubstituted phenyl, furyl, thienyl, C₁ -C₄ -alkylthienyl or pyridyl, and

R⁴ and R⁵ are identical or different and each is independently of the other C₁ -C₁₂ -alkyl, which may be interrupted by from 1 to 3 oxygen atoms and/or substituted by hydroxyl or phenyl,

with the proviso that in at least one of R¹, R⁴ and R⁵ the alkyl chain is interrupted by from 1 to 3 oxygen atoms, and to the use thereof for dyeing textile fibers.

DE-A-3 108 077 describes the dye 2-diethylamino-4-phenyl-5-(4'-chloro-5'-formylthiazol-2'-ylazo)thiazole.

DE-A-2 910 806 and JP-A-151 653/1982 disclose azo dyes where the coupling component is a thiazole derivative. Earlier patent applications EP-A-335 234 and DE-A-3 816 698 also disclose thiazole-azo dyes having a diazo component of the isothiazole series.

It is an object of the present invention to provide new azo dyes having a diazo component and a coupling component of the thiazole series which have an advantageous range of application properties.

We have found that this object is achieved by the above-defined thiazole-azo dyes of the formula I.

Any alkyl appearing in the abovementioned formula I may be either straight-chain or branched.

If substituted phenyl appears in the above-mentioned formula I, suitable substituents are for example C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, halogen, in particular chlorine or bromine, C₁ -C₄ -alkanoylamino and nitro.

Suitable, R¹, R², X¹ and X² are each for example methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl or sec-butoxycarbonyl.

R² is also for example CH═C(CN)₂ CH═C(CN)COOCH₃, CH═C(CN)COOC₂ H₅, CH═C(COOCH₃)₂ or CH═C(COOC₂ H₅)₂.

R¹ is further for example, like R³, R⁴ and R⁵, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secbutyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, heptyl, oxtyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, isodecyl, undecyl or dodecyl. (Isooctyl, isononyl and isodecyl are trivial names derived from the oxo synthesis alcohols - cf. Ullmanns Enzyklopadie der technischen Chemi, 4th edition, volume 7, pages 215 to 217, and volume 11, pages 435 and 436.)

R¹ is further for example chlorine or bromine.

R³ is further for example cyclopentyl, cyclohexyl, cycloheptyl, 2-, 3- or 4-methylcyclohexyl, 2-, 3- or 4-methylphenyl, 2-, 3- or 4-methoxyphenyl, 2-, 3- or 4-chlorophenyl, 2,4-dichlorophenyl, 2-, 3- or 4-bromophenyl, 2-, 3-or 4-formylaminophenyl, 2-, 3- or 4-acetylaminophenyl, 2-, 3- or 4-nitrophenyl or 5-methylthien-2-yl.

R¹, R³, R⁴ and R⁵ are each further for example 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-butoxyethyl, 2- or 3-methoxypropyl, 2- or 3-ethoxypropyl, 2- or 3-propoxypropyl, 2- or 3-butoxypropyl, 2- or 4-methoxybutyl, 2- or 4-ethoxybutyl, 2- or 4-propoxybutyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 4,8-dioxanonyl, 3,7-dioxaoctyl, 3,7-dioxanonyl, 4,7-dioxaoctyl, 4,7-dioxanonyl, 2- or 4-butoxybutyl, 4,8-dioxadecyl, 3,6,9-trioxadecyl or 3,6,9-trioxaundecyl.

R³, R⁴ and R⁵ are each further for example benzyl or 1- or 2-phenylethyl.

R⁴ and R⁵ are each further for example 2-hydroxyethyl, 2- or 3-hydroxypropyl or 2- or 4-hydroxybutyl.

R³ is further for example 2-phenoxybutyl, 3,6,9,12-tetraoxatridecyl or 3,6,9,12-tetraoxatetradecyl.

Preference is given to thiazole-azo dyes of the formula I where R⁴ and R⁵ are each independently of each other C₁ -C₆ alkyl which may be interrupted by 1 or 2 oxygen atoms.

Particular preference is given to those thiazoleazo dyes of the formula I where R⁴ is different than R⁵.

The thiazole-azo dyes according to the present invention are prepared in a conventional manner. For example, a 2-aminothiazole of the formula II ##STR3## where R¹ and R² are each as defined above, can be diazotized and coupled with a thiazole of the formula III ##STR4## where R⁴, R⁴ and R⁵ are each as defined above.

2-Aminothiazoles of the formula II are already known and described for example in US-A-4 395 544, or can be obtained in a similar manner to that described therein.

The thiazoles of the formula III are in general likewise known compounds. They are described for example in US-A-3 770 719 and in J.V. Metzger, Heterocyclic Compounds - Thiazole and its Derivatives, vol. 34, part 1, Interscience Publ., John Wiley, New York, 1979, or can be obtained by methods similar to those described therein.

Further details of the preparation of the dyes according to the present invention may be found in the Examples.

In general, those thiazole-azo dyes of the formula I where R⁴ and R⁵ together have four or more oxygen atoms are liquid at room temperature.

The novel thiazole-azo dyes of the formula I are advantageously used as disperse dyes for dyeing textile fibers, in particular cellulose esters or polyesters, and also polyamides or blends of polyesters and cellulose fibers.

The dyeings obtained have good fastness properties, in particular good light fastness. The novel dyes have good migration properties.

The Examples which follow further illustrate the invention.

EXAMPLE 1

16.25 g of 2-amino-4-chloro-5-formylthiazole were sprinkled into a mixture of 110 g of 90% strength by weight sulfuric acid, 17 g of glacial acetic acid and 32 g of 45% strength by weight nitrosyl sulfuric acid at 0°-3° C. The resulting solution was stirred at from -2° to 0° C. for 3.5 hours. The diazonium salt solution was then added to a 0° C. solution of 24 g of the coupling component of the formula ##STR5## in 200 ml of glacial acetic acid, 50 ml of propionic acid and 1 g of urea. During the addition of the diazonium salt solution, 70 g of sodium acetate were added at the same time while the temperature was maintained at <5° C. The coupling reaction, which proceeds even in strongly acidic solution, was complete within a few minutes. The resulting dye of the formula ##STR6## was filtered off with suction, washed and dried. 35 g were obtained of a bluish black, resinous dye which gives a reddish blue solution in N,N-dimethylformamide and dyes polyester fabric in bright reddish blue or navy shades. The absorption maximum of the dye, dissolved in 9:1 v/v N,N-dimethylformamide/glacial acetic acid, is 582 nm. The dyeings on polyester fabric are notable for very good light fastness, even in pale shades.

EXAMPLE 2

16.25 g of 2-amino-4-chloro-5-formylthiazole were diazotized as described in Example 1 and reacted with 24 g of the coupling component of the formula ##STR7## 31 g were obtained of a bluish green dye (absorption maximum 609 nm), which dyes polyester fabric in very light-fast greenish blue shades. The dye has the formula ##STR8##

EXAMPLE 3

Example 1 was repeated, except that the coupling component used was the furan derivative of the formula ##STR9## affording the greenish blue dye of the formula ##STR10## λ_(max) : 606 nm.

The same method was used to obtain the dyes of the formula ##STR11## listed in the following Table:

    __________________________________________________________________________     Example                                                                        No.  R.sup.3      R.sup.4                                                                              R.sup.5   Hue                                          __________________________________________________________________________      4   C.sub.6 H.sub.5                                                                             C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OCH.sub.3                                                                reddish blue                                  5   C.sub.6 H.sub.5                                                                             C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OC.sub.2 H.sub.5                                                         reddish blue                                  6   C.sub.6 H.sub.5                                                                             C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                               reddish blue                                  7   C.sub.6 H.sub.5                                                                             C.sub.3 H.sub.7 (n)                                                                  C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                               reddish blue                                  8   C.sub.6 H.sub.5                                                                             C.sub.3 H.sub.7 (n)                                                                  C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.2                                                reddish blue                                  9   C.sub.6 H.sub.5                                                                             C.sub.3 H.sub.7 (n)                                                                  C.sub.3 H.sub.6 OCH.sub.3                                                                reddish blue                                 10   C.sub.6 H.sub.5                                                                             C.sub.3 H.sub.7 (i)                                                                  C.sub.3 H.sub.6 OCH.sub.3                                                                reddish blue                                 11   C.sub.6 H.sub.5                                                                             C.sub.3 H.sub.7 (i)                                                                  C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                               reddish blue                                 12   C.sub.6 H.sub.5                                                                             C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OC.sub.2                                                reddish blue                                 13   C.sub.6 H.sub.5                                                                             C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.4 OCH.sub.3                                                                reddish blue                                 14   C.sub.6 H.sub.5                                                                             C.sub.3 H.sub.6 OCH.sub.3                                                            C.sub.3 H.sub.6 OCH.sub.3                                                                reddish blue                                 15   C.sub.6 H.sub.5                                                                             C.sub.3 H.sub.6 OCH.sub.3                                                            C.sub.3 H.sub.6 OC.sub.2 H.sub.5                                                         reddish blue                                 16                                                                                   ##STR12##   C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OCH.sub.3                                                                reddish blue                                 17                                                                                   ##STR13##   C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OC.sub.2 H.sub.5                                                         blue                                         18                                                                                   ##STR14##   C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OC.sub.2 H.sub.5                                                         blue                                         19                                                                                   ##STR15##   C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OC.sub.2 H.sub.5                                                         bluish green                                 20                                                                                   ##STR16##   C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OCH.sub.3                                                                bluish green                                 21                                                                                   ##STR17##   C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                         bluish green                                 22                                                                                   ##STR18##   C.sub.3 H.sub.7 (n)                                                                  C.sub.3 H.sub.6 OCH.sub.3                                                                bluish green                                 23                                                                                   ##STR19##   C.sub.3 H.sub.7 (n)                                                                  C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                               bluish green                                 24                                                                                   ##STR20##   C.sub.3 H.sub.7 (i)                                                                  C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                               bluish green                                 25                                                                                   ##STR21##   C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OC.sub.2 H.sub.5                                                         bluish green                                 26                                                                                   ##STR22##   C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OCH.sub.3                                                                reddish blue                                 27                                                                                   ##STR23##   C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OC.sub.2 H.sub.5                                                         reddish blue                                 28                                                                                   ##STR24##   C.sub.3 H.sub.7 (i)                                                                  C.sub.3 H.sub.6 OCH.sub.3                                                                reddish blue                                 29                                                                                   ##STR25##   C.sub.3 H.sub.7 (n)                                                                  C.sub.3 H.sub.6 OCH.sub.3                                                                reddish blue                                 30                                                                                   ##STR26##   C.sub.3 H.sub.7 (n)                                                                  C.sub.2 H.sub.4 OCH.sub.3                                                                reddish blue                                 31                                                                                   ##STR27##   C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                               reddish blue                                 32                                                                                   ##STR28##   C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.2                                                reddish blue                                 33                                                                                   ##STR29##   C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.2                                                bluish green                                 34                                                                                   ##STR30##   C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                               bluish green                                 35                                                                                   ##STR31##   C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OC.sub.2 H.sub.5                                                         bluish green                                 36                                                                                   ##STR32##   C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OCH.sub.3                                                                bluish green                                 37                                                                                   ##STR33##   C.sub.3 H.sub.7 (n)                                                                  C.sub.3 H.sub.6 OCH.sub.3                                                                bluish green                                 38                                                                                   ##STR34##   C.sub.3 H.sub.6 OCH.sub.3                                                            C.sub.3 H.sub.6 OCH.sub.3                                                                bluish green                                 39                                                                                   ##STR35##   C.sub.3 H.sub.6 OCH.sub.3                                                            C.sub.2 H.sub.5                                                                          reddish blue                                 40                                                                                   ##STR36##   C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                                dull bluish red                              41                                                                                   ##STR37##   C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.4 OCH.sub.3                                                                dull bluish red                              42                                                                                   ##STR38##   C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OCH.sub.3                                                                dull bluish red                              43                                                                                   ##STR39##   C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OC.sub.2 H.sub.5                                                         dull bluish red                              44                                                                                   ##STR40##   C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                               dull bluish red                              45                                                                                   ##STR41##   C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.2                                                dull bluish red                              46                                                                                   ##STR42##   C.sub.3 H.sub.7 (n)                                                                  C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.2                                                dull bluish red                              47                                                                                   ##STR43##   C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OCH.sub.3                                                                dull bluish red                              48   C.sub.6 H.sub.5 OCH.sub.2                                                                   C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OCH.sub.3                                                                dull bluish red                              49   C.sub.6 H.sub.5 OCH.sub.2                                                                   C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                               dull bluish red                              50                                                                                   ##STR44##   C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                               dull bluish red                              51   C.sub.6 H.sub.5 CH.sub.2                                                                    C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OC.sub. 2 H.sub.4 OCH.sub.3                                              dull bluish red                              52   C.sub.6 H.sub.5 CH.sub.2                                                                    C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OCH.sub.3                                                                dull bluish red                              53   C.sub.6 H.sub.5 CH.sub.2                                                                    C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                               dull bluish red                              54   C.sub.6 H.sub.5                                                                             C.sub.2 H.sub.4 OCH.sub.3                                                            CH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                        blue                                         __________________________________________________________________________ 

We claim:
 1. A thiazole-azo dye of the formula I ##STR45## where R¹ is C₁ -C₁₂ -alkyl, which may be interrupted by from 1 to 3 oxygen atoms, phenyl, halogen, cyano or C₁ -C₄ -alkoxycarbonyl, R² is formyl, cyano, C₁ -C₄ -alkoxycarbonyl or a radical of the formula --CH═CX¹ X², where X¹ and X² are identical or different and each is independently of the other cyano or C₁ -C₄ -alkoxycarbonyl,R³ is C₁ -C₁₂ -alkyl, which may be interrupted by from 1 to 4 oxygen atoms or substituted by phenyl or phenoxy, C₅ -C₇ -cycloalkyl, unsubstituted phenyl, furyl, thienyl, C₁ -C₄ -alkylthienyl or pyridyl, and R⁴ and R⁵ are identical or different and each is independently of the other C₁ -C₁₂ -alkyl, which may be interrupted by from 1 to 3 oxygen atoms and substituted by hydroxyl or phenyl or substituted by hydroxyl or phenyl with the proviso that in at least one of R¹ R⁴ and R⁵ the alkyl chain is interrupted by from 1 to 3 oxygen atoms.
 2. A thiazole-azo dye as claimed in claim 1, wherein R⁴ and R⁵ are each independently of the other C₁ -C₆ -alkyl which may be interrupted by 1 or 2 oxygen atoms. 